CN115448842B - Preparation method of diphenyl diamine type aromatic amine compound - Google Patents
Preparation method of diphenyl diamine type aromatic amine compound Download PDFInfo
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- CN115448842B CN115448842B CN202211039328.5A CN202211039328A CN115448842B CN 115448842 B CN115448842 B CN 115448842B CN 202211039328 A CN202211039328 A CN 202211039328A CN 115448842 B CN115448842 B CN 115448842B
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- benzidine
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- naphthyl
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- -1 diphenyl diamine Chemical class 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 235000010290 biphenyl Nutrition 0.000 title description 2
- 239000004305 biphenyl Substances 0.000 title description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 150000004982 aromatic amines Chemical class 0.000 claims abstract description 15
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims abstract description 13
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims abstract description 12
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 7
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 7
- 238000005859 coupling reaction Methods 0.000 claims abstract description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 125000001624 naphthyl group Chemical group 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- MWMNLUGPPZOPJQ-UHFFFAOYSA-N 4-(4-aminophenyl)-3-naphthalen-1-ylaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1C1=CC=CC2=CC=CC=C12 MWMNLUGPPZOPJQ-UHFFFAOYSA-N 0.000 claims description 27
- 238000001914 filtration Methods 0.000 claims description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 18
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000010992 reflux Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical group [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004537 pulping Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- LZWQNOHZMQIFBX-UHFFFAOYSA-N lithium;2-methylpropan-2-olate Chemical compound [Li+].CC(C)(C)[O-] LZWQNOHZMQIFBX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000010981 turquoise Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- FTDZECHQBVIHKZ-UHFFFAOYSA-N 5,5-dibromo-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(Br)(Br)CC=C1C1=CC=CC=C1 FTDZECHQBVIHKZ-UHFFFAOYSA-N 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- UDQLIWBWHVOIIF-UHFFFAOYSA-N 3-phenylbenzene-1,2-diamine Chemical compound NC1=CC=CC(C=2C=CC=CC=2)=C1N UDQLIWBWHVOIIF-UHFFFAOYSA-N 0.000 abstract 1
- MBPCKEZNJVJYTC-UHFFFAOYSA-N 4-[4-(n-phenylanilino)phenyl]aniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N(C=2C=CC=CC=2)C=2C=CC=CC=2)C=C1 MBPCKEZNJVJYTC-UHFFFAOYSA-N 0.000 description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 8
- 238000004811 liquid chromatography Methods 0.000 description 7
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910010272 inorganic material Inorganic materials 0.000 description 3
- 239000011147 inorganic material Substances 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/10—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
Abstract
A preparation method of biphenyl diamine type aromatic amine compound relates to the field of organic synthesis, which is a preparation method of benzidine shown in formula (I),
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of an aromatic amine compound.
Background
Organic electroluminescent diodes (OLEDs), which are a novel display technology, have the advantages of high brightness, high resolution, wide viewing angle (170 ° or more), flexibility, fast response speed, thin thickness, light weight, low power consumption, etc. Accordingly, OLEDs are increasingly receiving attention for flat panel display, lighting and backlighting applications. However, the industrialization process of the technology still faces a plurality of key problems, wherein the research work on the OLED molecular materials is an important trend for the research and development in the future. N-N-di (1-naphthyl) -benzidine and N, N-diphenyl benzidine are key intermediates in the synthesis process of OLED molecular materials. The existing preparation and purification methods of N-N-di (1-naphthyl) -benzidine and N, N-diphenyl benzidine need expensive palladium catalysts, have high cost and complex process, and have low yield of target products and more byproducts. The development of a preparation and purification method of N-N-di (1-naphthyl) -benzidine and N, N-diphenyl benzidine with simple process, high yield and few side reactions is a problem which is always desired to be solved in the industry.
Disclosure of Invention
The invention aims to obtain high-yield and high-purity N-N-di (1-naphthyl) -benzidine and N, N-diphenyl benzidine, so as to overcome the defects in the prior art.
In order to achieve the above object, the present invention adopts the technical scheme that:
A method for preparing benzidine shown in formula (I),
Wherein Ar is phenyl or naphthyl
Which comprises the following steps:
s1, mixing (1, 1 '-bis (diphenylphosphine) ferrocene) nickel dichloride, 1' -bis (diphenylphosphine) ferrocene and a Grignard reagent RMgX in an aromatic hydrocarbon solvent to obtain a first reaction mixture;
S2, adding aromatic amine, 4-dihalobiphenyl and alkali metal salt of alcohol into the first reaction mixture to carry out coupling reaction to obtain benzidine shown in the formula (I).
In some embodiments, the grignard reagent is selected from MeMgBr, meMgI, meMgCl, etMgCl, etMgBr, etMgI, and the aromatic hydrocarbon solvent is selected from benzene, toluene, xylene, or a combination thereof.
In some embodiments, the aromatic amine is aniline or 1-naphthylamine and the alkali metal salt of the alcohol is selected from potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium ethoxide, or sodium ethoxide, or a combination thereof.
In some embodiments, the coupling reaction is carried out at 60 ℃ to 95 ℃, preferably 70 ℃ to 85 ℃.
In some embodiments, the charge molar ratio between the (1, 1 '-bis (diphenylphosphine) ferrocene) dichloride nickel, 1' -bis (diphenylphosphine) ferrocene, and grignard reagent is 1:1 (2.0-6.0); the molar ratio of the aromatic amine, the 4, 4-dihalobiphenyl and the alkali metal salt of the alcohol is 1:1 (1.5-3.5).
In some embodiments, this includes purifying the aromatic amine of S2, dissolving the aromatic amine in a hydrocarbon solvent, heating to reflux, cooling, and filtering to obtain a purified aromatic amine.
In some embodiments, the molar ratio of aromatic amine to hydrocarbon solvent is 1:0.8 to 1:1.2, wherein the aromatic amine is 1-naphthylamine or 1-aniline, and the hydrocarbon solvent is selected from heptane, petroleum ether and the like.
In some embodiments, the method for purifying benzidine of formula (I) comprises purifying benzidine of formula (I) obtained in claim 1 in the presence of an organic solvent selected from toluene, methanol, THF, 1, 4-dioxane and an inorganic material; the inorganic material comprises distilled water and activated carbon.
In some embodiments, the method comprises the steps of subjecting benzidine shown in formula (I) to toluene leaching and filtering, then subjecting to methanol leaching and filtering, pulping with distilled water, then subjecting to water and methanol leaching and filtering, performing reduced pressure rotary drying to obtain a crude benzidine product shown in formula (I), dissolving the crude benzidine product with 1, 4-dioxane, adding active carbon for filtering, stirring and separating out filtrate at room temperature, filtering, and performing vacuum drying to obtain a purified benzidine product shown in formula (I).
Some embodiments provide a method for preparing N-bis (1-naphthyl) -benzidine or N, N-diphenyl benzidine, comprising the steps of:
S1, purifying 1-naphthylamine or 1-aniline;
s2, reacting (1, 1 '-bis (diphenylphosphine) ferrocene) nickel dichloride, 1' -bis (diphenylphosphine) ferrocene, toluene and MeMgBr to generate a first reaction mixture;
S3, reacting the purified 1-naphthylamine or 1-aniline, the first reaction mixture, 4-dibromobiphenyl and sodium tert-butoxide to generate N-N-di (1-naphthyl) -benzidine or N, N-diphenyl benzidine;
S4, purifying the N-N-di (1-naphthyl) -benzidine or N, N-diphenyl benzidine obtained in the S3 in the presence of an organic solvent and an inorganic material.
In one embodiment, in step S1, the purification is performed by heating 1-naphthylamine or 1-aniline in n-heptane to reflux, cooling, and filtering to obtain purified 1-naphthylamine or 1-aniline, wherein the molar ratio of 1-naphthylamine or 1-aniline to n-heptane is 1:0.8 to 1:10.
In one embodiment, step S1 further comprises the step of separating the purified 1-naphthylamine from the reaction mixture by filtration after the reaction is completed.
In one embodiment, step S1 further comprises the operation of testing the purity of the purified 1-naphthylamine by HPLC (Agilent liquid chromatography, model G7114A).
In one embodiment, the molar ratio of 1-naphthylamine, 4-dibromobiphenyl, to sodium tert-butoxide in step S3 is 2.4:1:1:2.8.
In one embodiment, step S3 further comprises the operation of monitoring whether the reaction is complete using thin layer chromatography at the time of reaction.
In one embodiment, the organic solvents described in step S4 are toluene, methanol, and THF, and are not limited thereto.
In one embodiment, step S4 further comprises the operation of testing the purity of the purified N, N-diphenyl benzidine by HPLC (Agilent liquid chromatography, model: G7114A).
In one embodiment, step S4 further comprises the operation of detecting the resulting reactant by nuclear magnetic resonance hydrogen spectrum 1H NMR(500MHz,DMSO-d6) delta
In one embodiment, step S1 is performed in an oil bath at 50 ℃.
In one embodiment, step S2 is performed at 0 ℃.
In one embodiment, steps S3, S4 are performed at 80 ℃.
In one embodiment, step S4 specifically includes: the N-N-di (1-naphthyl) -benzidine or N, N-diphenyl benzidine was filtered until slight cracks appear in the filter cake, 50mL of toluene was added to rinse the filter cake, 50mL of methanol was added to rinse the filter cake 2 times, and the filter cake was drained. The filter cake is beaten for 1 hour by 150mL distilled water, washed 3 times by 50mL water and 1 time by methanol, and dried under reduced pressure in a rotary way to obtain a crude earthy yellow product. 218mL of 1, 4-dioxane and/or THF was added to dissolve the crude product, the mixture was refluxed at 105℃for 30 minutes, 0.5g of activated carbon was added to reflux for 10 minutes, and the activated carbon and other insoluble matters were removed by filtration. The filtrate is stirred and separated out at room temperature, filtered and dried in vacuum to obtain the purified product.
Compared with the prior art, the application has at least the following beneficial effects: the provided preparation and purification method of the N-N-di (1-naphthyl) -benzidine and the N, N-diphenyl benzidine adopts a new route, has the advantages of short process route, simple operation, mild condition, environment friendliness, low cost, high yield of target products and few byproducts, and is suitable for industrial production of the preparation and purification method of the N-N-di (1-naphthyl) -benzidine and the N, N-diphenyl benzidine. The benzidine shown in the formula (I) is N-N-di (1-naphthyl) -benzidine or N, N-diphenyl benzidine, and the HPLC purity of the purified product is more than 99.5%.
Detailed Description
In view of the shortcomings of the prior art, the inventor of the present application has long studied and practiced to propose the technical scheme of the present application, namely, a preparation and purification method of N-N-di (1-naphthyl) -benzidine and N, N-diphenyl benzidine. In a more typical embodiment, the process route of the preparation method is as follows:
the reagents and materials, unless otherwise specified, are commercially available.
EXAMPLE 1 preparation of N-N-bis (1-naphthyl) -benzidine
Ni (dppf) Cl 2 (about 5 mmol) and dppf (about 5 mmol) were weighed and dissolved in toluene (about 150 mL), meMgBr (about 20 mmol) was added dropwise at 0℃and stirred at room temperature for 10 minutes to give a first reaction mixture, 4-dibromobiphenyl (about 50 mmol), purified 1-naphthylamine (about 120 mmol) and sodium t-butoxide (about 140 mmol) were added to the first reaction mixture, and stirred at 80℃for 6 hours. After the reaction is completed, a dark green solid is separated out, the reaction is cooled to room temperature, and filtered to a filter cake, so that the product N-N-di (1-naphthyl) -benzidine is obtained, and the yield is 100%.
EXAMPLE 2 preparation of N, N-diphenyl benzidine
Ni (dppf) Cl 2 (about 10 mmol) and dppf (about 10 mmol) were weighed and dissolved in toluene (about 300 mL), meMgBr (about 40 mmol) was added dropwise at 0℃and stirred at room temperature for 10 minutes to give a first reaction mixture, 4-dibromobiphenyl (about 100 mmol), 1-aniline (about 100 mmol) and sodium t-butoxide (about 280 mmol) were added to the first reaction mixture, and stirred at 80℃for 6 hours. After the reaction is completed, a dark green solid is separated out, the reaction is cooled to room temperature, and filtered to a filter cake, so that the product N, N-diphenyl benzidine is obtained.
Example 3a process for the preparation and purification of N-bis (1-naphthyl) -benzidine comprises the steps of:
S1, weighing 1-naphthylamine (about 280 mmol) and dissolving in n-heptane (280 mL), carrying out oil bath at 50 ℃ for 30 minutes, refluxing until solid is dissolved, separating the solid and the n-heptane into two phases, naturally cooling and stirring the mixture to room temperature, filtering the mixture, and carrying out vacuum drying to obtain 37.2g of a product (purity=99.8%, yield=85%), and drying and storing the product in a nitrogen environment. Characterization results of this purified 1-naphthylamine HPLC (agilent liquid chromatography, model: G7114A): the method comprises 50-50CH 3CN-H2 O30 mins; the sample injection amount is 2 mu L; flow rate 0.8mL; the column temperature was 35℃and the wavelength was 305nm. Retention time = 7.4min, purity = 99.8%.
S2, ni (dppf) Cl 2 (about 5 mmol) and dppf (about 5 mmol) were weighed and dissolved in toluene (about 150 mL), meMgBr (about 20 mmol) was added dropwise at 0℃and stirred at room temperature for 10 minutes to obtain a first reaction mixture.
S3, 4-dibromobiphenyl (about 50 mmol), purified 1-naphthylamine (about 120 mmol), and sodium t-butoxide (about 140 mmol) were added to the first reaction mixture, and stirred at 80℃for 6 hours. After the reaction is completed, a dark green solid is separated out, the reaction is cooled to room temperature, and filtered to obtain a filter cake, thus obtaining 31g of crude N-N-di (1-naphthyl) -benzidine.
S4, adding 50mL of toluene to soak and wash the filter cake, and filtering the filter cake. The filter cake was rinsed 2 times with 50mL methanol and dried. The filter cake was slurried with 150mL of distilled water for 1 hour, the salts were removed, 50mL of water was washed 3 times, methanol was 1 time, the water in the product was removed, and rotary drying was performed under reduced pressure to obtain 21.52g of a crude product of earthy yellow (purity=99.50%, yield=98.7%). Characterization of the crude turquoise product HPLC (Agilent liquid chromatograph, model: G7114A): the method comprises the steps of 50-50THF-H 2 O60 mins; the sample injection amount is 2 mu L; flow rate 0.8mL; the column temperature was 35℃and the wavelength was 305nm. Retention time = 23min.436
S5, adding 172mL (8V) of 1, 4-dioxane to dissolve crude products, refluxing at 105 ℃ for 30 minutes, adding 0.5g of activated carbon to reflux for 10 minutes, and filtering to remove the activated carbon and other insoluble substances. The filtrate was stirred at room temperature to precipitate, filtered and dried under vacuum to give 18.4g of purified N-bis (1-naphthyl) -benzidine (purity=99.80%, total yield of five steps=85.1%). : characterization results of this purified N-N-bis (1-naphthyl) -benzidine HPLC (Agilent liquid chromatography, model: G7114A): the method comprises the steps of 50-50THF-H 2 O60 mins; the sample injection amount is 2 mu L; flow rate 0.8mL; the column temperature was 35℃and the wavelength was 305nm. Retention time = 23min.
Example 4 the purification method of N-N-bis (1-naphthyl) -benzidine provided in this example comprises the following steps:
S1, adjusting the amounts of crude N-N-di (1-naphthyl) -benzidine and 1, 4-dioxane to N-N-di (1-naphthyl) -benzidine (10 g,23 mmol) and 1, 4-dioxane 80mL (8V) respectively, dissolving the crude product of 1, 4-dioxane, refluxing at 105 ℃ for 30 minutes, adding 0.5g of activated carbon, refluxing for 10 minutes, and filtering. The filtrate was naturally cooled and stirred to precipitate, cooled to room temperature, and then ice-bathed for 1 hour and stirred to precipitate, filtered and dried in vacuo to obtain 7.1g of purified N-N-di (1-naphthyl) -benzidine.
The final purity of N-N-bis (1-naphthyl) -benzidine in this example was 99.87% and the yield was 71%. Characterization results of this purified N-bis (1-naphthyl) -benzidine HPLC (agilent liquid chromatography, model: G7114A): the method comprises the steps of 50-50THF-H2O 60mins; the sample injection amount is 2 mu L; flow rate 0.8mL; the column temperature was 35℃and the wavelength was 305nm. Retention time = 21.098min. Characterization of the purified N-N-bis (1-naphthyl) -benzidine 1H NMR(500MHz,DMSO-d6)δ7.10-7.40(m,4H),7.26-7.35(m,2H),7.36-7.45(m,2H),7.46-7.70(m,10H),7.85-8.00(m,2H),8.20-8.24(m,2H),8.28(s,2H).
Example 5 the method for preparing and purifying N, N-diphenyl benzidine provided in this example comprises the steps of:
S1, ni (dppf) Cl 2 (about 10 mmol) and dppf (about 10 mmol) were weighed and dissolved in toluene (about 300 mL), meMgBr (about 40 mmol) was added dropwise at 0℃and stirred at room temperature for 10 minutes to obtain a first reaction mixture.
S2, 4-dibromobiphenyl (about 100 mmol), 1-aniline (about 100 mmol), and sodium t-butoxide (about 280 mmol) were added to the first reaction mixture, and stirred at 80℃for 6 hours. After the reaction is completed, a dark green solid is separated out, the reaction is cooled to room temperature, and the product N, N-diphenyl benzidine is obtained after filtration.
S3 the purification procedure was the same as in step S4 of example 1, yielding 35.04g of crude yellow product (purity=96.65%, yield=104.2%). Characterization of the crude product was HPLC (agilent liquid chromatography, model: G7114A): the method comprises the steps of 50-50THF-H2O 60mins; the sample injection amount is 2 mu L; flow rate 0.8mL; column temperature 35 ℃, wavelength 305nm, retention time = 23min.
Example 6 the purification method of N, N-diphenyl benzidine provided in this example includes the following steps:
S1, pulping crude N, N-diphenyl benzidine (35.04 g) and 70mL (2V) THF at room temperature for 30 minutes. The impurities were removed by filtration, the filter cake was washed once with THF and dried under vacuum to give 30.5g of purified N, N-diphenyl benzidine. The final purity of N, N-diphenyl benzidine in this example was 99.53%, and the total yield was 90.7%. The characterization of the purified N, N-diphenyl benzidine was HPLC (Agilent liquid chromatography, model: G7114A): the method comprises the steps of 50-50THF-H 2 O60mins; the sample injection amount is 2 mu L; flow rate 0.8mL; column temperature 35 ℃, wavelength 305nm, retention time = 15.776min. The characterization result of the product is that 1H NMR(500MHz,DMSO-d6)δ6.75-6.91(m,2H),7.00-7.21(m,8H),7.22-7.34(m,4H),7.40-7.60(m,4H),8.15-8.33(m,2H).
While the application has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for those of the embodiments without departing from the spirit and scope of the application. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the application without departing from the scope thereof. Therefore, it is intended that the application not be limited to the particular embodiment disclosed for carrying out this application, but that the application will include all embodiments falling within the scope of the appended claims.
Claims (6)
1. A method for preparing benzidine shown in formula (I),
(I)
Wherein Ar is phenyl or naphthyl,
Which comprises the following steps:
s1, mixing (1, 1 '-bis (diphenylphosphine) ferrocene) nickel dichloride, 1' -bis (diphenylphosphine) ferrocene and a Grignard reagent RMgX in an aromatic hydrocarbon solvent to obtain a first reaction mixture;
S2, adding an aromatic amine, 4-dihalobiphenyl and alkali metal salt of alcohol into the first reaction mixture to carry out coupling reaction to obtain benzidine shown in a formula (I);
The grignard reagent is selected from MeMgBr, meMgI, meMgCl, etMgCl, etMgBr, etMgI, and the aromatic hydrocarbon solvent is selected from benzene, toluene, xylene, or a combination thereof;
The feeding mole ratio of the (1, 1 '-bis (diphenylphosphine) ferrocene) nickel dichloride to the 1,1' -bis (diphenylphosphine) ferrocene to the Grignard reagent is 1:1 (2.0-6.0); the molar ratio of the aromatic amine, the 4, 4-dihalobiphenyl and the alkali metal salt of the alcohol is 1:1 (1.5-3.5).
2. The process of claim 1, wherein the aromatic amine is aniline or 1-naphthylamine and the alkali metal salt of the alcohol is selected from the group consisting of potassium tert-butoxide, sodium tert-butoxide, lithium tert-butoxide, sodium methoxide, potassium ethoxide, and sodium ethoxide, or a combination thereof.
3. The method of claim 1, wherein the coupling reaction is carried out at 60 o C to 95 o C.
4. The method of claim 3, wherein the coupling reaction is carried out at 70 o C to 85 o C.
5. The process of claim 1, comprising purifying the aromatic amine of S2, dissolving the aromatic amine in a hydrocarbon solvent, heating to reflux, cooling, and filtering to obtain a purified aromatic amine.
6. A method for preparing N-N-di (1-naphthyl) -benzidine, comprising the following steps:
S1, weighing 1-naphthylamine, dissolving in n-heptane, placing in 50 o C oil bath for 30 minutes, refluxing until solid is dissolved, separating the solid from n-heptane into two phases, naturally cooling and stirring to room temperature, filtering, drying in vacuum to obtain a product, and drying and storing in a nitrogen environment;
S2, weighing Ni (dppf) Cl 2 and dppf, dissolving in toluene, dropwise adding MeMgBr at 0 o ℃, and stirring at room temperature to obtain a first reaction mixture;
S3, adding 4, 4-dibromobiphenyl, purified 1-naphthylamine and sodium tert-butoxide into the first reaction mixture, stirring at 80 o ℃, completely reacting, precipitating dark green solid, cooling the reaction to room temperature, and filtering to obtain a filter cake to obtain crude N-N-di (1-naphthyl) -benzidine;
s4, adding toluene to soak and wash a filter cake, filtering to obtain a filter cake, adding methanol to soak and wash the filter cake for 2 times, filtering, pulping the filter cake with distilled water for 1 hour, removing salts, washing with water for 3 times and methanol for 1 time, removing water in the product, and performing reduced pressure rotary drying to obtain a turquoise crude product;
S5, adding 1, 4-dioxane to dissolve crude products, refluxing for 30 minutes at 105 ℃, adding active carbon to reflux for 10 minutes, filtering to remove active carbon and other insoluble substances, stirring and separating out filtrate at room temperature, filtering, and drying in vacuum.
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